Flavoring materials



Patented Jan. 18, 1949 FLAVORING MATERIALS Wendell W. Moyer, Decatur,111., asslgnor to A. E.

Staley Manufacturing Company, Decatur, Ill., a corporation of DelawareNo Drawing. Application May 19, 1947, Serial No. 749,087

2 Claims; 1

This invention relates to improvements in the preparation of flavoringmaterials. More particularly, it has to do with novel methods for improving the aroma and flavor of unfermented liquid flavoring materialsresembling the condiment known as soy sauce.

Genuine soy sauce is made by a fermentation process requiring from abouttwo months to several years to complete. The fermented liquid has acharacteristic pleasant aroma and flavor. In

,preparation of soy sauce, chemical hydrolysis general, the saucesprepared by the longer fermentations have superior aroma and flavor.

Unfermented sauces resembling soy sauce may be prepared by hydrolyzingprotein materials with a hot aqueous solution of hydrochloric acid. Aliquid product similar to fermented saucethen can be recovered from thehydrolyzed mixture by neutralizing the latter with a sodium base andfiltering it to remove insoluble matter. Preferred sources of rawprotein are soybeans, wheat, and

milk. Other proteins, such as those present in corn, peanuts, andmeatmay also be used. Preparation of a sauce by hydrochloric aciddigestion of a mixture of soybeans and wheat is described at pages 92-94of the July, 1945, issue of Food Industries (Vol.17, No. '7, pages758-360). Preparaalone of the protein raw material has two principaladvantages. The preparation time is reduced from a minimum of about twomonths to a maximum of two or three days, and the liquid productobtained is much richer in amino acids and other soluble proteinhydrolytic products. Ofisetting these advantages, however, is the factthat the chemical sauce lacks the characteristic aroma and flavor of thefermented kind. The aroma and flavor of the chemical sauce are notunpleasant, but they are distinctly unlike those qualities of afermented sauce.

Although the fermentation aroma and flavor -of soy sauce may berelatively unimportant with respect to some uses of the sauce andsimilar liquid flavoring materials, such as those dependent solely uponcolor and salt content, they are quite important with respect to others.For extions oi similar liquid products are described in I United StatesPatents No. 1,992,462 and No. attests.

It has also been proposed to combine chemical hydrolysis of the proteinraw material with sub sequent fermentation of the neutralizedhydrolyaate. For example, according to United States Patent No.2,107,133, an acid hydrolyzed liquid product is first prepared fromprotein material, preferably soybean meal, then it is mixed with roastedwheat or equivalent cereal and fermented in a manner conventional forsoy sauce. It is pointed out in this patent that the overall time ofsauce production is greatly shortened by the acid precligestion, andthat preferably the acid treatment should not completely hydrolyze theproteinmaterlalto constituent amino acids. Even so, the shortenedfermentation still requires several weeks, and the entire sauce has tobe stored during that period. Also, according to Japanese Patent No.91,407, equal parts of soybean or other vegetable protein materials areseparately hydrolyzed with equal volume of hot 10 percent hydrochloricacid and hot 10 percent sodium hydroxide solutions, the hydrolyzates aremixed, filtered, and the approximately neutral filtrate is fermented forabout one month with yeast and other materials.

Compared with the conventional fermentation ample, since thefermentation aroma and flavor have long been associated with genuine soysauce, they have become important criteria in the users evaluation ofthe product, and generally are important factors in the users enjoymentof it.

Combining chemical hydrolysis of the protein material with subsequentfermentation oi the hydrolyzate may tend to overcome the aroma andflavor disadvantages of the straight chemical sauce and may also reducethe fermentation time required by the conventional soy sauce process,but it still requires a preparation time that is quite long comparedwith that of a chemical sauce.

In a co-pending application being filed concurrently herewith, it isdisclosed that the aroma and flavor oi unfermentedliquid flavoringmaterials resembling soy sauce are distinctly improved by addingrelatively small proportions of suitably fermented sugar solution-s tothe unfermented flavoring material. It is also disclosed in thatapplication that if the sugar solution to be fermented lacks suflicientnitrogenous and mineral constituents to support vigorous growth of themicroorganisms, these nutrient materials may be added to it. Citedexamples of such added nutrient materials are peptone and yeast extract.Cited examples of sugar-containing solutions easily fermentable withoutaddition of the nutrients are refinery cane molasses and black strapmolasses. L

Generally, the objects of the present invention are the same as those ofthe above mentioned copending application, namely, to improve the aromaand flavor of unfermented liquid flavoring materials similar to soysauce, and to reduce the preparation time and liquid storage facilitiesrequired in the conventional fermentation of soy sauce and in themodified conventional fermentation process comprising chemicalhydrolysis of the protein material followed by fermentation of thehydrolyzate.

Briefly the objects of this invention are attained by fermenting a sugarsolution containing a minor proportion of a protein hydrolyzate for arelatively short time under suitable conditions and then adding a smallproportion of the fermented solution to the unfermented liquid flavoringmaterial.

More specifically, it is an object of the presentinvention to provide aprocess wherein the. sugar solution to be fermented is supplemented withaminor proportion of protein hydrolyzate to obtain two importantadvantages, namely,,aroma and flavor improvements produced in the baseflavoring material which are superior to those obtained by the methodsdisclosed in the aforementioned application, and elimination of ex-Other objects of the invention will in part be obvious and will in partappear hereinafter.

' culture fermentations are employed, altho under The inventionaccordingly comprises the several steps'and the relation of one or moreof such steps with respect to each of the others thereof, which will beexemplified in the process hereinafter disclosed, and the scope of theapplication of which will be indicated in the claims.

Preferably, the supplemental protein hydrolyzate is chosen, for example,from the unfermented base flavoring material to which the fermentedsugar solution is to be added. This preference is based on convenience.It is to be understood, however, that the sugar-containing solution tobe fermented may be supplemented with protein'hydrolyzates other thanthat represented by the base unfermented flavoring material. Also, thesupplemental protein hydrolyzate maybe one.obtained by partial or bycomplete hydrolysis of the protein to its constituent amino acids.Furthermore, the hydrolysis may have been catalyzed by acids, alkalies,proteolytic enzymes or combinations of these agencies, and the resultinghydrolyzate may or may not contain appreciable proportions of inorganicsalts formed in part by neutralization of the hydrolyzing acid or base.It is unnecessary that the supplemental protein hydrolyzate be preparedfrom protein substantially free of non-protein material. Such crudeprotein raw materials as soybean meal, corn gluten, and peanut meal aresuitable for the purposes of this invention.

The preferred ratio of added protein hydrolytic products to sugar solidsin the mixture to be fermented lies within the range of about 1 to 2percent. Beneficial results due to supplementation of the sugarsolutionwith the protein hydrolytic products may be obtained, however, at aratio of protein to sugar as low as 0.1 percent and as high as fivepercent. In calculating these ratios, dry substance weights of therespective materials are to be used. The supplemental proteinhydrolyzate may be either dilute or concentrated with respect to proteinhydrolytic products. Preferably, it contains not less than about 5percent hydrolyzed protein, so that addition of enough of it to thesugar solution to provide the preferred ratio of hydrolyzed protein tosugar solids will not markedly dilute the sugar solution.

It is stated in the above mentioned tic-p nding liquid flavoringmaterials can be provided.

Yeasts, especially the osmophilic kind, constitute the preferred classof microorganisms for fermenting the sugar solution. Certain molds and.bacteria can also be used. Preferably, pure some conditions a wild" ornature fermentation of the sugar solution will be satisfactory.

Osmophilic yeasts in general are also satisfactory in practicing thepresent invention. Preferably, but not necessarily, the yeast should begrown in a sugar solution containing from about to about 50 percentsolids. This keeps down the size of the fermenter required for a givenproduction of flavoring material, and eliminates the need ofconcentrating the fermented liquor, with attending danger of losingimportant aroma and flavor principles, beforeit is added to the basematerial. Another advantage in growing the osmophilic yeasts in theabove specified concentrations of substrate is that such concentrationsinhibit the concurrent growth of undesirable molds and bacteria, andthus eliminate the need of sterilizing the sugar solution beforehand.

The preferred molds are those suitable in the conventional fermentationpreparation of soy sauce. Many of these are osmophilic and can be usedin the concentrated'sugar solutions, as

indicated above, without sterilizing the solution beforehand. If anon-osmophilic mold is used with a more diluted sugar solution, itshould be sterilized beforehand to prevent formation of undesirableodors and flavors by growth of improper molds and bacteria.

Unidentified microaerophilic bacteria isolated from fermenting molasseshave been found to be satisfactory fermenting agents for the sugarsolution.

A preferred type of sugar-containing solution to be fermented and usedin accordance with this invention is the mother liquor or molassesobtained in the refining of crude cane sugar. The optimum concentrationrange of this molasses, when being fermented with an osmophilic yeast,is about to about 40 percent solids. It can be successfully fermented,however, at higher and lower concentrations. The upper practical limitis about percent solids. Above this concentra- 7,

tion, only a few microorganisms will grow and produce the desired aromaand flavor principles sugar solution lacks sufllcient nitrogenous andmineral constituents for suitable growth of the microorganisms, thesenutrient materials may be teriol may alter the latter undesirably inseveral ways. The maximum permissible proportion oi added sugar solutionwill depend, of course, upon its nature and the way it blends with thebase material. From 1 to 10 percent by weight of the fermented sugarsolution, based on the unfermented base sauce, is usually suflicient,but it is to be understood that the present invention is not limited tothis range of proportions.

it is advantageous to use a sugar medium whose iiavor and aroma arecompatible with the base flavoring material. Refinery cane molasses andblack strap molasses are particularly suitable for this reason.

The invention is illustrated by the following examples in which allparts are by weight unless otherwise specified.

Example .2

Unfermented liquid sauce similar to soy sauce was prepared by aciddigestion of soybean meal according to directions given in United StatesPatent No. 1092462. A mixture of is parts of refinery cane molasses and1 part of the unfermented sauce was diluted with water to 40 percentsolids, was inoculated with a culture of Zyyosaccharomyces nussbaumeriand incubated for five days at i F. The molasses acquired a strongfermentation odor and flavor. Addition of a parts of the fermentedmolasses to 94 parts Same as Example 1 but substituting a sugar solutioncontaining 30 percent sucrose by weight for the diluted refinerymolasses. The aroma and flavor of the base sauce were distinctly alteredto resemble more nearly those two properties of fermented soy sauce.

Example 3 Same as Example 1 but substituting a sugar solution containing20 percent dextrose by weight for the diluted refinery molasses. Thearoma and flavor of the base sauce were improved to about the samedegree as in Example 2.

Example 4 Same as Example 1. but substituting a 10.5 B. starchconversion liquor having a dextrose equivalent of 55 and a fermentableextract of 50 for the diluted refinery molasses. The improvement in thearoma and flavor of the base sauce was about the same as that obtainedin Examples 2 and 3.

Example 5 A mixture of 119 parts of refinery cane molasses and 1 partsauce prepared according to U. S.

Patent No. 1,992,462, diluted with water to 20 percent solids, wasinoculated with a strain oi. Aspergillus flavus and incubated at 90 F.for

- eleven days. Addition of 8 parts of the fermented The addition oflarge proportions of material.

molasses to 92 parts of the base sauce used in Example 1 distinctlyimproved the aroma and flavor of the latter, making it more nearlyresemble fermented soy sauce in those two respects.

Example 6 A mixture of 19 parts of refinery cane molasses and 1 partsauce prepared according to U. 8. Patent No. l,992,i62, diluted withwater to 10 percent solids, was inoculated with an unidentifiedmicroaerophilic bacterium isolated from fermenting refinery canemolasses and in- Example 7 Same as Example 1 except that the base sauceused therein was replaced by an unfermcnted sauce prepared by aciddigestion of a mixture of soybeans and wheat according to directionsgiven at pages 92-94: of the July, 19%, issue of b ood Industries. Thearoma and flavor of the base sauce were markedly improved, being changedtoresemble quite closely those two properties of genuine soy sauce.

Example 8 Same as Example 1 except that the base sauce was replaced byan unfermented sauce prepared by acid digestion of casein according tothe di rections given in United States Patent No. 2,049,576. Theimprovement in the aroma and flavor of the base sauce was about the sameas that obtained in Example 1.

It will be apparent to those acquainted with the fermentation of sugarsby molds, yeasts, and bacteria, that many such fermentations, especiallythose performed by molds and bacteria, will yield odors and flavorsunsuited to the purpose of this invention. For example, bacteria of thegenus Clostridia are in general undesirable, and some strains ofAspergz'llus niger yield unpalatable odors and flavors duringfermentation. No broad claim is made to improving the flavor and aromaof unfermented liquid flavoring materials similar to soy sauce by addingthereto a relatively small proportion of a solution resulting from thefermentation of a sugar-containing solution by any mold, yeast, orbacteria. Determination of the suitability of the fermented sugarsolution for the purpose of this invention is based on compatibility ofthe aroma and flavor of the fermented solution with the unfermented baseI have found that if the aroma and flavor of the fermented sugarsolution are not unpleasant or disagreeable alone, addition of suchfermented solution to the unfermented base solution improves the aromaand flavor of the latter. It is to be pointed out also that thecriterion of usefulness of the fermented sugar solution is notnecessarily that the aroma and flavor of the solution shall resemblethose two properties of fermented soy sauce. As mentioned earlier, theblending of the aromas and flavors is not simply additive. Frequently afermented sugar solution having a strong fermentation odor'and flavor,neither one disagreeable but neither one similar to the correspondingproperty 01' fermented soy sauce, provides a pronounced improvement inthe base material, 1. e., makes its aroma and flavor strongly resemblethose two properties of fermented soy sauce.

As used hereinbefore, and in the appended claims, the verb "ferment andits derivatives refer to the action and eflects of growingmicroorganisms selected from the group consisting of molds, yeasts, andbacteria.

Likewise the expression uniermented liquid flavoring material similar tosoy sauce" refers to palatable aqueous solutions derived principallyfrom protein raw material by means other than the action ofmicroorganisms. Usually, in the preparation of such flavoring materials,the proteln raw material is hydrolyzed with hot dilute hydrochloricacid, then neutralized with a sodium base, and filtered. It is to beunderstood, however, thatothermeans are available. For example, theprotein raw material may be hydrolyzed with a sodium base, thenneutralized with hydrochloric acid. Or, the protein material may behydrolyzed with an acid whose unpalatable anion can be removed as aninsoluble material. Examples of this would be hydrolysis with sulfuricor phosphoric acid followed by neutralization with lime. Again, theprotein raw material may be hydrolyzed with any selected acid or base,the hydrolyzate neutralized with any selected base or acid. and theunpalatable anions and cations removed with ion exchange materials.

Since certain changes may be made in carrying out the above processwithout departing from the scope of the invention, it is intended thatall matter contained in the above description shall be interpreted asillustrative and not in a limiting sense.

It is also to be understood that the following claims are intended tocover all of the generic and specific features of the invention hereindescribed, and all statements of the scope of the invention which, as amatter of lan uage, might be said to fall therebetween.

I claim:

1. In the production of chemically prepared soy sauce-type condimentwhich comprises providin a base or uniermented chemically preparedliquid flavoring material, providing a sugar-containin solution andadding thereto protein hydrolytic products to the extent of 0.1 to 5 percent based on the sugar solids, fermenting said solution until itdevelops an aroma and flavor compatible with said base material, andadding to said base material a relatively small proportion of saidfermented solution, whereby the aroma and flavor oi the condiment areimproved.

2. In the production of chemically prepared soy sauce-type condimentwhich comprises providing a base or unfermented chemically preparedliquid flavoring material, providing a auger-containin solution andadding thereto a portion of said base material containing proteinhydrolytic products to the extent oi not less than 0.1 per cent and notmore than 5 per cent of the sugar solids, fermenting said solution untilit develops an aroma and flavor compatible with said base material, andadding to said base material a relatively small proportion of saidfermented solution, whereby the aroma and flavor oi the condiment areim- Proved.

WENDEIL W. MOYER.

' REFERENCES crrnn The following references are of record in the file ofthis patent:

UNITED STATES PA'I'E'NI'S FDREIGN PATENTS Country Date Great BritainApr. 5, 1940 OTHER REFERENCES The Microbiology of Foods, by Tanner,second ed. Published in Champaign, Illinois, by Gar- Number Number rardPress, 1944. pages 752 and 753.

